Catalysts comprising salan ligands

ABSTRACT

Catalysts comprising salan ligands with carbazole moieties. Also, catalyst systems comprising the catalyst and an activator; methods to prepare the ligands, catalysts and catalyst systems; processes to polymerize olefins using the catalysts and/or catalyst systems; and the olefin polymers prepared according to the processes.

RELATED APPLICATIONS

This application claims priority to and the benefit of provisionalapplication U.S. 61/679,488, filed Aug. 3, 2012.

NAMES OF PARTIES TO JOINT RESEARCH AGREEMENT

(1) ExxonMobil Chemical Company, A Division of ExxonMobil Corporation;(2) Ramot at Tel Aviv University Ltd.

FIELD OF THE INVENTION

This invention relates to novel catalyst compounds comprising Salanligands and catalyst systems comprising such and uses thereof.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

There is a need in the art for new and improved catalysts and catalystsystems to obtain new and improved polyolefins, polymerizationprocesses, and the like. Accordingly, there is a need in the art for newand improved catalyst systems for the polymerization of olefins for oneor more of the following purposes: to achieve one or more specificpolymer properties, such as high polymer melting point and/or highpolymer molecular weights; to increase conversion or comonomerincorporation; and/or to alter comonomer distribution withoutdeterioration of the properties of the resulting polymer. The instantdisclosure is directed to novel catalyst compounds, catalysts systemscomprising such compounds, and processes for the polymerization ofolefins using such compounds and systems in satisfaction of the need inthe art.

SUMMARY OF THE INVENTION

The instant disclosure is directed to catalyst compounds, catalystsystems comprising such compounds, processes for the preparation of thecatalyst compounds and systems, and processes for the polymerization ofolefins using such catalyst compounds and systems.

In an embodiment, the catalyst compound comprises Group 3, 4, 5 and/or 6disubstituted compounds supported by a heteroaryl-substitutedtetradentate di-anionic Salan ligand.

In an embodiment, a catalyst compound is represented by the formula:

where:

each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

M is a Group 3, 4, 5 or 6 transition metal;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; and

Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

In an embodiment, a catalyst system comprises an activator and acatalyst compound represented by the formula:

where:

M is a Group 3, 4, 5 or 6 transition metal;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or a combination thereof, or X¹ and X² jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure,provided, however, where M is trivalent then X² is not present;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; and

Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

In an embodiment, a process to polymerize olefins comprises:

contacting one or more olefins with a catalyst system at a temperature,a pressure, and for a period of time sufficient to produce a polyolefin,the catalyst system comprising an activator and a catalyst compoundrepresented by the formula:

where:M is a Group 3, 4, 5 or 6 transition metal;each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; andY is a divalent C₁ to C₂₀ hydrocarbyl.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in Chem. Eng.News, 1985, 63, 27. Therefore, a “Group 4 metal” is an element fromGroup 4 of the Periodic Table.

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, an arrow indicates that the bond may bedative, and each dashed line represents a bond having varying degrees ofcovalency and a varying degree of coordination.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document unless otherwisespecified. For purposes of this disclosure, a hydrocarbyl radical isdefined to be C₁ to C₇₀ radicals, or C₁ to C₂₀ radicals, or C₁ to C₁₀radicals, or C₆ to C₇₀ radicals, or C₆ to C₂₀ radicals, or C₇ to C₂₀radicals that may be linear, branched, or cyclic where appropriate(aromatic or non-aromatic); and includes hydrocarbyl radicalssubstituted with other hydrocarbyl radicals and/or one or morefunctional groups comprising elements from Groups 13-17 of the periodictable of the elements. In addition two or more such hydrocarbyl radicalsmay together form a fused ring system, including partially or fullyhydrogenated fused ring systems, which may include heterocyclicradicals.

The term “substituted” means that a hydrogen atom and/or a carbon atomin the base structure has been replaced with a hydrocarbyl radical,and/or a functional group, and/or a heteroatom or a heteroatomcontaining group. Accordingly, the term hydrocarbyl radical includesheteroatom containing groups. For purposes herein, a heteroatom isdefined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group, which is the base structure,substituted with a methyl radical, which may also be referred to as amethyl functional group, ethyl alcohol is an ethyl group, which is thebase structure, substituted with an —OH functional group, and pyridineis a phenyl group having a carbon in the base structure of the benzenering substituted with a nitrogen atom.

For purposes herein, a hydrocarbyl radical may be independently selectedfrom substituted or unsubstituted methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butyryl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, andtriacontynyl.

For purposes herein, hydrocarbyl radicals may also include isomers ofsaturated, partially unsaturated and aromatic cyclic structures whereinthe radical may additionally be subjected to the types of substitutionsdescribed above. The term “aryl”, “aryl radical”, and/or “aryl group”refers to aromatic cyclic structures, which may be substituted withhydrocarbyl radicals and/or functional groups as defined herein.Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl,acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl,benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls,benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl,carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl,fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl,indolinyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl,methyl benzyl, methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl,purinyl, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl,pyrimidinyl, pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl,thiazolyl, thiophenyl, and the like.

It is to be understood that for purposes herein, when a radical islisted, it indicates that the base structure of the radical (the radicaltype) and all other radicals formed when that radical is subjected tothe substitutions defined above. Alkyl, alkenyl, and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers,for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compounds having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

Likewise the terms “functional group”, “group” and “substituent” arealso used interchangeably throughout this document unless otherwisespecified. For purposes herein, a functional group includes both organicand inorganic radicals or moieties comprising elements from Groups 13,14, 15, 16, 17 of the periodic table of elements. Suitable functionalgroups may include hydrocarbyl radicals, e.g., alkyl radicals, alkeneradicals, aryl radicals, and/or halogen (Cl, Br, I, F), O, S, Se, Te,NR*_(x), OR*, SeR*, TeR*, PR*_(x), AsR*_(x), SbR*_(x), SR*, BR*_(x),SiR*_(x), GeR*_(x), SnR*_(x), PbR*_(x), and/or the like, wherein R is aC₁ to C₂₀ hydrocarbyl as defined above and wherein x is the appropriateinteger to provide an electron neutral moiety. Other examples offunctional groups include those typically referred to as amines, imides,amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides,halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, andthe like.

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have an “ethylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or different“mer” units. A “homopolymer” is a polymer having mer units that are thesame. A “copolymer” is a polymer having two or more mer units that aredifferent from each other. A “terpolymer” is a polymer having three merunits that are different from each other. “Different” in reference tomer units indicates that the mer units differ from each other by atleast one atom or are different isomerically. Accordingly, thedefinition of copolymer, as used herein, includes terpolymers and thelike. An oligomer is typically a polymer having a low molecular weight,such an Mn of less than 25,000 g/mol, or in an embodiment less than2,500 g/mol, or a low number of mer units, such as 75 mer units or less.An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymercomprising at least 50 mole % ethylene derived units, a “propylenepolymer” or “propylene copolymer” is a polymer or copolymer comprisingat least 50 mole % propylene derived units, and so on.

For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₂olefins. Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst”, “catalyst compound”, and “transition metalcompound” are defined to mean a compound capable of initiatingpolymerization catalysis under the appropriate conditions. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor. A “catalyst system”is combination of at least one catalyst compound, at least oneactivator, an optional co-activator, and an optional support material,where the system can polymerize monomers to polymer. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components it iswell understood by one of ordinary skill in the art that the ionic formof the component is the form that reacts with the monomers to producepolymers.

For purposes herein the term “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours; andmay be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat⁻¹hr⁻¹. Conversion is the amount of monomer that isconverted to polymer product, and is reported as mol % and is calculatedbased on the polymer yield and the amount of monomer fed into thereactor. Catalyst activity is a measure of how active the catalyst isand is reported as the mass of product polymer (P) produced per mole ofcatalyst (cat) used (kg P/mol cat).

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Inan embodiment a co-activator can be pre-mixed with the catalyst compoundto form an alkylated catalyst compound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) unless statedotherwise, Mw is weight average molecular weight determined by gelpermeation chromatography (GPC), and Mz is z average molecular weightdetermined by GPC, wt % is weight percent, and mol % is mole percent.Molecular weight distribution (MWD) is defined to be Mw divided by Mn.Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz,are g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butylrefers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butylis normal butyl, pMe is para-methyl, Bz is benzyl, THF istetrahydrofuran, Mes is mesityl, also known as 1,3,5-trimethylbenzene,Tol is toluene, TMS is trimethylsilyl, TIBAL is triisobutylaluminum,TNOAL is triisobutyl n-octylaluminum, MAO is methylalumoxane, and MOMOis methoxymethoxy (also referred to as methoxymethyl ether).

For purposes herein, RT is room temperature, which is defined as 25° C.unless otherwise specified. All percentages are weight percent (wt %)unless otherwise specified.

In the description herein, the salan catalyst may be described as acatalyst precursor, a pre-catalyst compound, salan catalyst compound ora transition metal compound, and these terms are used interchangeably.

Catalyst Compounds

In an embodiment, the catalyst comprises Group 3, 4, 5 and/or 6disubstituted compounds supported by a tetradentate di-anionic salanligand, useful to polymerize olefins and/or α-olefins to producepolyolefins and/or poly(α-olefins).

In an embodiment, the catalyst compounds are represented by the formula:

wherein:

A and A′ are heteroaryl radicals;

M is a Group 3, 4, 5 or 6 transition metal;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;

each R¹, R², R³, R⁴, R⁵, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁷, and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²¹ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; and

Y and Z together form a divalent C₁ to C₂₀ hydrocarbyl radical.

In an embodiment, A and A′ each comprise carbazole radicals.

In an embodiment, the catalyst compounds are represented by thefollowing structure:

where:

each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

M is a Group 3, 4, 5 or 6 transition metal covalently bonded to eachoxygen atom, and bonded with varying degrees of covalency andcoordination to each of nitrogen atoms N¹ and N²;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl, a functional groupcomprising elements from Group 13-17 of the periodic table of theelements, or independently, may join together to form a C₄ to C₆₂ cyclicor polycyclic ring structure, or a combination thereof; and

Y is a divalent hydrocarbyl radical covalently bonded to and bridgingbetween both of the nitrogen atoms N¹ and N². In an embodiment, two ormore of R¹ to R²⁸ may independently join together to form a C₄ to C₆₂cyclic or polycyclic ring structure.

In an embodiment, M is a Group 4 metal, or M is Hf, Ti and/or Zr, or Mis Hf or Zr. In an embodiment, each of X¹ and X² is independentlyselected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides having from 1 to 20carbon atoms, sulfides, phosphides, halides, amines, phosphines, ethers,an combinations thereof.

In an embodiment, X¹ and X² together form a part of a fused ring or aring system having from 4 to 62 carbon atoms.

In an embodiment, each of X¹ and X² is independently selected from thegroup consisting of halides, alkyl radicals having from 1 to 7 carbonatoms, benzyl radicals, or a combination thereof.

In an embodiment, Y is a divalent C₁-C₂₀ hydrocarbyl radical comprisinga portion that comprises a linker backbone comprising from 1 to 18carbon atoms linking or bridging between nitrogen atoms N¹ and N². In anembodiment, Y is a C₁-C₂₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*) or N(R*), wherein each R* is independently aC₁-C₁₈ hydrocarbyl. In an embodiment, Y is selected from the groupconsisting of ethylene (—CH₂CH₂—) and 1,2-cyclohexylene, and/or—CH₂CH₂CH₂— derived from propylene. In an embodiment, Y is —CH₂CH₂CH₂—derived from propylene.

In an embodiment, each X is, independently, a halogen or a C₁ to C₇hydrocarbyl radical.

In an embodiment, each X is a benzyl radical. In an embodiment, each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical,or a C₁ to C₁₀ hydrocarbyl radical. In an embodiment, one or more of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is a methylradical, a fluoride, or a combination thereof.

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ aremethyl radicals; R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and Yis ethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶ and R¹⁸through R²⁸ are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ aremethyl radicals; R⁴ and R¹⁷ are fluoro (F) functional groups; R², R³, R⁵through R¹³, R¹⁵, R¹⁶ and R¹⁸ through R²⁸ are hydrogen; and Y isethylene (—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are tert-butylradicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,R²⁰, R²², R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen; and Y is ethylene(—CH₂CH₂—).

In an embodiment, M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²²,R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment, two or more different catalyst compounds are presentin the catalyst system used herein. In an embodiment, two or moredifferent catalyst compounds are present in the reaction zone where theprocess(es) described herein occur. When two transition metal compoundbased catalysts are used in one reactor as a mixed catalyst system, thetwo transition metal compounds are chosen such that the two arecompatible. Compatible catalysts are those catalysts having similarkinetics of termination and insertion of monomer and comonomer(s) and/ordo not detrimentally interact with each other. For purposes herein, theterm “incompatible catalysts” refers to and means catalysts that satisfyone or more of the following:

1) those catalysts that when present together reduce the activity of atleast one of the catalysts by greater than 50%;

2) those catalysts that under the same reactive conditions producepolymers such that one of the polymers has a molecular weight that ismore than twice the molecular weight of the other polymer; and

3) those catalysts that differ in comonomer incorporation or reactivityratio under the same conditions by more than about 30%. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. In an embodiment, the catalyst systems use thesame activator for the catalyst compounds. In an embodiment, two or moredifferent activators, such as a non-coordinating anion activator and analumoxane, can be used in combination. If one or more catalyst compoundscontain an X¹ or X² ligand which is not a hydride, or a hydrocarbyl,then in an embodiment the alumoxane is contacted with the catalystcompounds prior to addition of the non-coordinating anion activator.

In an embodiment, when two transition metal compounds (pre-catalysts)are utilized, they may be used in any ratio. In an embodiment, a molarratio of a first transition metal compound (A) to a second transitionmetal compound (B) will fall within the range of (A:B) 1:1000 to 1000:1,or 1:100 to 500:1, or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or5:1 to 50:1. The particular ratio chosen will depend on the exactpre-catalysts chosen, the method of activation, and the end productdesired. In an embodiment, when using two pre-catalysts, where both areactivated with the same activator, useful mole percents, based upon thetotal moles of the pre-catalysts, are 10:90 to 0.1:99, or 25:75 to 99:1,or 50:50 to 99.5:0.5, or 50:50 to 99:1, or 75:25 to 99:1, or 90:10 to99:1.

Methods to Prepare the Catalyst Compounds.

In an embodiment, the transition metal compounds may be prepared by twogeneral synthetic routes. In an embodiment, the parent salan ligands maybe prepared by a one-step Mannich reaction from the parent phenol(reaction A) or by a two-step imine-condensation/alkylation procedure ifan aldehyde located ortho to a hydroxy functional group (e.g., asubstituted salicylaldehyde base structure) is used (reaction B).

The salan ligand is then converted into the metal di-substitutedcatalyst precursor by reaction with the metal tetra-substituted startingmaterial to yield the finished complex. In an embodiment, the salanligand is then converted into the metal dibenzyl catalyst precursor byreaction with the metal tetra-aryl starting material, e.g., tetrabenzyl,to yield the finished complex (reaction C).

Activators

The terms “cocatalyst” and “activator” are used interchangeably todescribe activators and are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Activators may includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl radical. Examplesof alumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the catalyst precursor compound comprises anabstractable ligand which is an alkyl, halide, alkoxide or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. In an embodiment, visually clear methylalumoxane may be used. Acloudy or gelled alumoxane can be filtered to produce a clear solutionor clear alumoxane can be decanted from the cloudy solution. A usefulalumoxane is a modified methyl alumoxane (MMAO) described in U.S. Pat.No. 5,041,584 and/or commercially available from Akzo Chemicals, Inc.under the trade designation Modified Methylalumoxane type 3A. Solidalumoxanes may also be used.

When the activator is an alumoxane (modified or unmodified), in anembodiment, the maximum amount of activator at a 5000-fold molar excessAl/M over the catalyst compound (per metal catalytic site). In anembodiment, the minimum activator-to-catalyst-compound, which isdetermined according to molar concentration of the transition metal M,in an embodiments is 1 mole aluminum or less to mole of transition metalM. In an embodiment, the activator comprises alumoxane and the alumoxaneis present at a ratio of 1 mole aluminum or more to mole of catalystcompound. In an embodiment, the minimum activator-to-catalyst-compoundmolar ratio is a 1:1 molar ratio. Other embodiments of Al:M rangesinclude from 1:1 to 500:1, or from 1:1 to 200:1, or from 1:1 to 100:1,or from 1:1 to 50:1.

In an embodiment, little or no alumoxane (i.e., less than 0.001 wt %) isused in the polymerization processes described herein. In an embodiment,alumoxane is present at 0.00 mole %, or the alumoxane is present at amolar ratio of aluminum to catalyst compound transition metal less than500:1, or less than 300:1, or less than 100:1, or less than 1:1.

The term “non-coordinating anion” (NCA) refers to an anion which eitherdoes not coordinate to a cation, or which is only weakly coordinated toa cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible with the polymerization or catalyst system, stabilize thetransition metal cation in the sense of balancing its ionic charge at+1, and yet are sufficiently labile to permit displacement duringpolymerization.

In an embodiment, an ionizing or stoichiometric activator may be used,which may be neutral or ionic, such as tri(n-butyl) ammonium boronmetalloid precursor, polyhalogenated heteroborane anions (WO 98/43983),boric acid (U.S. Pat. No. 5,942,459), or a combination thereof. In anembodiment, neutral or ionic activators alone or in combination withalumoxane or modified alumoxane activators may be used.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups or radicals can be the same or differentand in an embodiment are each independently selected from substituted orunsubstituted alkyls, alkenyls, alkyns, aryls, alkoxy, and halogens. Inan embodiment, the three groups are independently selected from halogen,mono or multicyclic (including halosubstituted) aryls, alkyls, andalkenyl compounds, and mixtures thereof; or independently selected fromalkenyl radicals having 1 to 20 carbon atoms, alkyl radicals having 1 to20 carbon atoms, alkoxy radicals having 1 to 20 carbon atoms and aryl orsubstituted aryl radicals having 3 to 20 carbon atoms. In an embodiment,the three substituent groups are alkyl radicals having 1 to 20 carbonatoms, phenyl, naphthyl, or mixtures thereof. In an embodiment, thethree groups are halogenated aryl groups, e.g., fluorinated aryl groups.In an embodiment the neutral stoichiometric activator is trisperfluorophenyl boron or tris perfluoronaphthyl boron.

In an embodiment, ionic stoichiometric activator compounds may includean active proton, or some other cation associated with, but notcoordinated to, or only loosely coordinated to the remaining ion of theionizing compound. Suitable examples include compounds and the likedescribed in European publications EP 0 570 982 A; EP 0 520 732 A; EP 0495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A; U.S. Pat.Nos. 5,153,157; 5,198,401; 5,066,741; 5,206,197; 5,241,025; 5,384,299;5,502,124; and WO 1996/04319; all of which are herein fully incorporatedby reference.

In an embodiment compounds useful as an activator comprise a cation,which is, for example, a Bronsted acid capable of donating a proton, anda compatible non-coordinating anion which anion is relatively large(bulky), capable of stabilizing the active catalyst species (the Group 4cation, e.g.) which is formed when the two compounds are combined andsaid anion will be sufficiently labile to be displaced by olefinic,diolefinic or acetylenically unsaturated substrates or other neutralLewis bases, such as ethers, amines, and the like. Two classes of usefulcompatible non-coordinating anions are disclosed in EP 0 277,003 A1, andEP 0 277,004 A1, which include anionic coordination complexes comprisinga plurality of lipophilic radicals covalently coordinated to andshielding a central charge-bearing metal or metalloid core; and anionscomprising a plurality of boron atoms such as carboranes,metallacarboranes, and boranes.

In an embodiment, the stoichiometric activators include a cation and ananion component, and may be represented by the following formula (1):(Z)_(d) ⁺(A^(d−))  (1)wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe catalyst precursor, resulting in a cationic transition metalspecies, or the activating cation (L-H)_(d) ⁺ is a Bronsted acid,capable of donating a proton to the catalyst precursor resulting in atransition metal cation, including ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof, or ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxoniums from ethers, such as dimethyl ether diethylether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid it may be represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, thereducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component A^(d−) include those having theformula [M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5or 6, or 3, 4, 5 or 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements, or boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl radicals, said Q having up to 20 carbonatoms with the proviso that in not more than one occurrence is Q ahalide, and two Q groups may form a ring structure. Each Q may be afluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Qis a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable A^(d−) components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment, this invention relates to a method to polymerizeolefins comprising contacting olefins (e.g., ethylene) with a salancatalyst compound, a chain transfer agent (CTA) and a boron containingNCA activator represented by the formula (1) where: Z is (L-H) or areducible Lewis acid; L is an neutral Lewis base (as further describedabove); H is hydrogen; (L-H) is a Bronsted acid (as further describedabove); A^(d−) is a boron containing non-coordinating anion having thecharge d⁻ (as further described above); d is 1, 2, or 3.

In an embodiment in any of the NCA's represented by Formula 1 describedabove, the anion component A^(d−) is represented by the formula[M*^(k*+)Q*_(n*)]^(d*−) wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5,or 6 (or 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independentlyselected from hydride, bridged or unbridged dialkylamido, halogen,alkoxide, aryloxide, hydrocarbyl radicals, said Q* having up to 20carbon atoms with the proviso that in not more than 1 occurrence is Q* ahalogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with a salan catalyst compound asdescribed above, optionally with a CTA and an NCA activator representedby the Formula (2):R^(n)M**(ArNHal)_(4-n)  (2)where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SR¹, —NR² ₂, and —PR³₂, where each R¹, R², or R³ is independently a C₁ to C₃₀ hydrocarbyl asdefined above; or a C₁ to C₃₀ hydrocarbyl substituted organometalloid.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA also comprises cation comprising areducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph₃C+), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA may also comprise a cationrepresented by the formula, (L-H)_(d) ⁺, wherein L is an neutral Lewisbase; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or(L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated byreference herein.

In an embodiment, an activator useful herein comprises a salt of acationic oxidizing agent and a noncoordinating, compatible anionrepresented by the Formula (3):(OX^(e+))_(d)(A^(d−))_(e)  (3)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In an embodiment, the salan catalyst compounds, CTA's, and/or NCA'sdescribed herein can be used with bulky activators. A “bulky activator”as used herein refers to anionic activators represented by the formula:

where:each R¹ is, independently, a halide, or a fluoride;each R² is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl radical or a siloxy group of the formula —O—Si—R^(a), whereR^(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl radical (or R² is afluoride or a perfluorinated phenyl radical);each R³ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl radicalor a siloxy group of the formula —O—Si—R^(a), where R^(a) is a C₁ to C₂₀hydrocarbyl radical or hydrocarbylsilyl group (or R³ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl radical); wherein R² and R³ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (or R² and R³ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, or greater than 300 cubicÅ, or greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular MV Per Total Structure of Formula of subst. MV Activator boronsubstituents each substituent (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl) borate

C₁₀F₇ 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl) borate

C₁₂F₉ 349 1396 [4-tButyl—PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 515 2060

Exemplary bulky activators useful in catalyst systems herein include:

-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   [4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in    U.S. Pat. No. 7,297,653, which is fully incorporated by reference    herein.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes according to the instantdisclosure include:

-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(tert-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,-   tropillium tetraphenylborate,-   triphenylcarbenium tetraphenylborate,-   triphenylphosphonium tetraphenylborate,-   triethylsilylium tetraphenylborate,-   benzene(diazonium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   tropillium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   triethylsilylium tetrakis(pentafluorophenyl)borate,-   benzene(diazonium)tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,-   dimethyl(tert-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(tert-butyl)ammonium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,    and-   dialkyl ammonium salts, such as:-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate; and    additional tri-substituted phosphonium salts, such as    tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and    tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate.

Suitable activators include:

-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(perfluorophenyl)borate,-   [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻];    1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;    and tetrakis(pentafluorophenyl)borate,    4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such astriphenylcarbenium tetraphenylborate,

-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate,

-   N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trialkylammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate,-   trialkylammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate,-   trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,    (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or    tert-butyl).

In an embodiment, any of the activators described herein may be mixedtogether before or after combination with the catalyst compound and/orCTA and/or NCA, or before being mixed with the catalyst compound and/orCTA, and/or NCA.

In an embodiment two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In an embodiment, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment, the NCA activator-to-catalyst ratio is a 1:1 molarratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to1000:1. In an embodiment, the NCA activator-to-catalyst ratio is 0.5:1to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined withcombinations of alumoxanes and NCA's (see for example, U.S. Pat. No.5,153,157, U.S. Pat. No. 5,453,410, EP 0 573 120 B1, WO 94/07928, and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

Scavengers or Co-Activators

In an embodiment the catalyst system may further include scavengersand/or co-activators. Suitable aluminum alkyl or organoaluminumcompounds which may be utilized as scavengers or co-activators include,for example, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like. Other oxophilicspecies such as diethyl zinc may be used. In an embodiment, thescavengers and/or co-activators are present at less than 14 wt %, orfrom 0.1 to 10 wt %, or from 0.5 to 7 wt %, by weight of the catalystsystem.

Catalyst Supports

In an embodiment, the catalyst system may comprise an inert supportmaterial. In an embodiment, the support material comprises a poroussupport material, for example, talc, and/or inorganic oxides. Othersuitable support materials include zeolites, clays, organoclays, or anyother organic or inorganic support material and the like, or mixturesthereof.

In an embodiment, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in catalystsystems herein include Groups 2, 4, 13, and 14 metal oxides, such assilica, alumina, and mixtures thereof. Other inorganic oxides that maybe employed either alone or in combination with the silica, and/oralumina include magnesia, titania, zirconia, montmorillonite,phyllosilicate, and/or the like. Other suitable support materialsinclude finely divided functionalized polyolefins, such as finelydivided polyethylene.

In an embodiment, the support material may have a surface area in therange of from about 10 to about 700 m²/g, pore volume in the range offrom about 0.1 to about 4.0 cc/g and average particle size in the rangeof from about 5 to about 500 μm, or the surface area of the supportmaterial is in the range of from about 50 to about 500 m²/g, pore volumeof from about 0.5 to about 3.5 cc/g and average particle size of fromabout 10 to about 200 μm. In an embodiment, a majority portion of thesurface area of the support material is in the range is from about 100to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. In an embodiment,the average pore size of the support material is in the range of from 10to 1000 Å, or 50 to about 500 Å, or 75 to about 350 Å. In an embodiment,the support material is a high surface area, amorphous silica having asurface area greater than or equal to about 300 m²/gm, and/or a porevolume of 1.65 cm³/gm. Suitable silicas are marketed under thetradenames of Davison 952 or Davison 955 by the Davison ChemicalDivision of W.R. Grace and Company. In an embodiment the support maycomprise Davison 948.

In an embodiment, the support material should be essentially dry, thatis, essentially free of absorbed water. Drying of the support materialcan be effected by heating or calcining at about 100° C. to about 1000°C., or at a temperature of at least about 400° C., or 500° C., or 600°C. When the support material is silica, it is heated to at least 200°C., or about 200° C. to about 850° C., or at least 600° C. for a time ofabout 1 minute to about 100 hours, or from about 12 hours to about 72hours, or from about 24 hours to about 60 hours. In an embodiment, thecalcined support material must have at least some reactive hydroxyl (OH)groups to produce supported catalyst systems according to the instantdisclosure.

In an embodiment, the calcined support material is contacted with atleast one polymerization catalyst comprising at least one catalystcompound and an activator. In an embodiment, the support material,having reactive surface groups, typically hydroxyl groups, is slurriedin a non-polar solvent and the resulting slurry is contacted with asolution of a catalyst compound and an activator. In an embodiment, theslurry of the support material is first contacted with the activator fora period of time in the range of from about 0.5 hours to about 24 hours,or from about 2 hours to about 16 hours, or from about 4 hours to about8 hours. The solution of the catalyst compound is then contacted withthe isolated support/activator. In an embodiment, the supported catalystsystem is generated in situ. In alternate embodiment, the slurry of thesupport material is first contacted with the catalyst compound for aperiod of time in the range of from about 0.5 hours to about 24 hours,or from about 2 hours to about 16 hours, or from about 4 hours to about8 hours. The slurry of the supported catalyst compound is then contactedwith the activator solution.

In an embodiment, the mixture of the catalyst, activator and support isheated to about 0° C. to about 70° C., or to about 23° C. to about 60°C., or to room temperature. Contact times typically range from about 0.5hours to about 24 hours, or from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator and the catalyst compound are at leastpartially soluble and which are liquid at reaction temperatures.Suitable non-polar solvents include alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In an embodiment, a polymerization processes includes contactingmonomers (such as ethylene and propylene), and optionally comonomers,with a catalyst system comprising an activator and at least one catalystcompound, as described above. In an embodiment, the catalyst compoundand activator may be combined in any order, and may be combined prior tocontacting with the monomer. In an embodiment, the catalyst compoundand/or the activator are combined after contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, or C₂ to C₂₀ alpha olefins, or C₂ to C₁₂ alpha olefins,or ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene and isomers thereof. In an embodimentof the invention, the monomer comprises propylene and an optionalcomonomers comprising one or more ethylene or C₄ to C₄₀ olefins, or C₄to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers maybe linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In anembodiment, the monomer comprises ethylene or ethylene and a comonomercomprising one or more C₃ to C₄₀ olefins, or C₄ to C₂₀ olefins, or C₆ toC₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, or hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, ornorbornene, norbornadiene, and dicyclopentadiene.

In an embodiment one or more dienes are present in the polymer producedherein at up to 10 weight %, or at 0.00001 to 1.0 weight %, or 0.002 to0.5 weight %, or 0.003 to 0.2 weight %, based upon the total weight ofthe composition. In an embodiment 500 ppm or less of diene is added tothe polymerization, or 400 ppm or less, or 300 ppm or less. In anembodiment at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, or C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).In an embodiment, the diolefin monomers may be selected from alpha,omega-diene monomers (i.e. di-vinyl monomers). More or, the diolefinmonomers are linear di-vinyl monomers, most or those containing from 4to 30 carbon atoms. Examples of dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weightpolybutadienes (Mw less than 1000 g/mol). Cyclic dienes includecyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene,divinylbenzene, dicyclopentadiene or higher ring containing diolefinswith or without substituents at various ring positions.

In an embodiment, where butene is the comonomer, the butene source maybe a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Polymerization processes according to the instant disclosure may becarried out in any manner known in the art. Any suspension, homogeneous,bulk, solution, slurry, or gas phase polymerization process known in theart can be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Homogeneous polymerization processes and slurryprocesses are suitable for use herein, wherein a homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media. A bulk homogeneousprocess is suitable for use herein, wherein a bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 volume % or more. In an embodiment, no solvent or diluent is presentor added in the reaction medium, (except for the small amounts used asthe carrier for the catalyst system or other additives, or amountstypically found with the monomer; e.g., propane in propylene). In anembodiment, the process is a slurry process. As used herein the term“slurry polymerization process” means a polymerization process where asupported catalyst is employed and monomers are polymerized on thesupported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In an embodiment, aliphatic hydrocarbonsolvents are used as the solvent, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof. In an embodiment, the solvent is not aromatic, or aromatics arepresent in the solvent at less than 1 wt %, or less than 0.5 wt %, orless than 0.0 wt % based upon the weight of the solvents.

In an embodiment, the feed concentration of the monomers and comonomersfor the polymerization is 60 vol % solvent or less, or 40 vol % or less,or 20 vol % or less, based on the total volume of the feedstream. Or thepolymerization is run in a bulk process.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Suitable temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., or about 20° C. to about 200° C., or about 35° C. toabout 150° C., or from about 40° C. to about 120° C., or from about 45°C. to about 80° C.; and at a pressure in the range of from about 0.35MPa to about 10 MPa, or from about 0.45 MPa to about 6 MPa, or fromabout 0.5 MPa to about 4 MPa.

In an embodiment, the run time of the reaction is from about 0.1 minutesto about 24 hours, or up to 16 hours, or in the range of from about 5 to250 minutes, or from about 10 to 120 minutes.

In an embodiment, hydrogen is present in the polymerization reactor at apartial pressure of 0.001 to 50 psig (0.007 to 345 kPa), or from 0.01 to25 psig (0.07 to 172 kPa), or 0.1 to 10 psig (0.7 to 70 kPa).

In an embodiment, the activity of the catalyst is at least 50g/mmol/hour, or 500 or more g/mmol/hour, or 5000 or more g/mmol/hr, or50,000 or more g/mmol/hr. In an alternate embodiment, the conversion ofolefin monomer is at least 10%, based upon polymer yield and the weightof the monomer entering the reaction zone, or 20% or more, or 30% ormore, or 50% or more, or 80% or more.

In an embodiment, the polymerization conditions include one or more ofthe following: 1) temperatures of 0 to 300° C. (or 25 to 150° C., or 40to 120° C., or 45 to 80° C.); 2) a pressure of atmospheric pressure to10 MPa (or 0.35 to 10 MPa, or from 0.45 to 6 MPa, or from 0.5 to 4 MPa);3) the presence of an aliphatic hydrocarbon solvent (such as isobutane,butane, pentane, isopentane, hexanes, isohexane, heptane, octane,dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, suchas cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof; or where aromatics are or present in the solvent atless than 1 wt %, or less than 0.5 wt %, or at 0 wt % based upon theweight of the solvents); 4) wherein the catalyst system used in thepolymerization comprises less than 0.5 mol %, or 0 mol % alumoxane, orthe alumoxane is present at a molar ratio of aluminum to transitionmetal less than 500:1, or less than 300:1, or less than 100:1, or lessthan 1:1; 5) the polymerization or occurs in one reaction zone; 6) theproductivity of the catalyst compound is at least 80,000 g/mmol/hr (orat least 150,000 g/mmol/hr, or at least 200,000 g/mmol/hr, or at least250,000 g/mmol/hr, or at least 300,000 g/mmol/hr); 7) scavengers (suchas trialkyl aluminum compounds) are absent (e.g., present at zero mol %)or the scavenger is present at a molar ratio of scavenger to transitionmetal of less than 100:1, or less than 50:1, or less than 15:1, or lessthan 10:1; and/or 8) optionally hydrogen is present in thepolymerization reactor at a partial pressure of 0.007 to 345 kPa (0.001to 50 psig) (or from 0.07 to 172 kPa (0.01 to 25 psig), or 0.7 to 70 kPa(0.1 to 10 psig)).

In an embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Inan embodiment, the polymerization occurs in one reaction zone.

Polyolefin Products

The instant disclosure also relates to compositions of matter producedby the methods described herein.

In an embodiment, the process described herein produces propylenehomopolymers or propylene copolymers, such as propylene-ethylene and/orpropylene-α-olefin (or C₃ to C₂₀) copolymers (such as propylene-hexenecopolymers or propylene-octene copolymers) having a Mw/Mn of greaterthan 1 to 4 (or greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers, orpolyethylene and polypropylene homopolymers and copolymers. In anembodiment, the polymers produced herein are homopolymers of ethylene orpropylene, are copolymers of ethylene or having from 0 to 25 mole % (orfrom 0.5 to 20 mole %, or from 1 to 15 mole %, or from 3 to 10 mole %)of one or more C₃ to C₂₀ olefin comonomer (or C₃ to C₁₂ alpha-olefin, orpropylene, butene, hexene, octene, decene, dodecene, or propylene,butene, hexene, octene), or are copolymers of propylene or having from 0to 25 mole % (or from 0.5 to 20 mole %, or from 1 to 15 mole %, or from3 to 10 mole %) of one or more of C₂ or C₄ to C₂₀ olefin comonomer (orethylene or C₄ to C₁₂ alpha-olefin, or ethylene, butene, hexene, octene,decene, dodecene, or ethylene, butene, hexene, octene).

In an embodiment, the monomer is ethylene and the comonomer is hexene,or from 1 to 15 mole % hexene, or 1 to 10 mole % hexene.

In an embodiment, the polymers produced herein have an Mw of 5,000 to1,000,000 g/mol (e.g., 25,000 to 750,000 g/mol, or 50,000 to 500,000g/mol), and/or an Mw/Mn of greater than 1 to 40, or 1.2 to 20, or 1.3 to10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.

In an embodiment, the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromotography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 2006/0173123 page 24-25, paragraphs [0334] to [0341].

In an embodiment, the polymers may be linear in character, which may bedetermined by elution fractionation, wherein non-linear polymers have aCDBI of less than 45%, whereas linear polyethylene types refer topolyethylene having a CDBI of greater than 50%, the CDBI beingdetermined as described in WO93/03093 (U.S. Pat. No. 5,206,075). In anembodiment the polymer produced herein has a composition distributionbreadth index (CDBI) of 50% or more, or 60% or more, or 70% or more.CDBI is a measure of the composition distribution of monomer within thepolymer chains and is measured by the procedure described in PCTpublication WO 93/03093, published Feb. 18, 1993, specifically columns 7and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20,p. 441 (1982) and U.S. Pat. No. 5,008,204, including that fractionshaving a weight average molecular weight (Mw) below 15,000 are ignoredwhen determining CDBI.

Polymers with an Mw/Mn of 4.5 or less may include a significant level oflong chain branching. The long chain branching is understood to be theresult of the incorporation of terminally unsaturated polymer chains(formed by the specific termination reaction mechanism encountered withsingle site catalysts) into other polymer chains in a manner analogousto monomer incorporation. The branches are hence believed to be linearin structure and may be present at a level where no peaks can bespecifically attributed to such long chain branches in the ¹³C NMRspectrum. In an embodiment, the polymers produced according to theinstant disclosure comprise a significant amount of long chainbranching, defined as having a ratio of long chain branching of at least7 carbons per 1000 carbon atoms as determined according to the ¹³C NMRspectrum of greater than 0.5. In an embodiment, the ratio of long chainbranching with branches having at least 7 carbons, per 1000 carbon atomsas determined according to the ¹³C NMR spectrum is greater than 1, orgreater than 1.5, or greater than 2.

In an embodiment, the polymers produced according to the instantdisclosure include a significant amount of vinyl termination, defined asa ratio of vinyl groups per molecule of greater than or equal to 0.2. Inan embodiment, the polymers according to the instant disclosure comprisea ratio of vinyl groups per molecule of greater than or equal to 0.5, or0.7, or 0.8, or 0.9, or 0.95, when determined according to thedescription provided in the J. American Chemical Soc., 114, 1992, pp.1025-1032, or an equivalent thereof.

Blends

In an embodiment, the polymer (or the polyethylene or polypropylene)produced herein is combined with one or more additional polymers priorto being formed into a film, molded part or other article. Other usefulpolymers include polyethylene, isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene, and/or butene, and/or hexene, polybutene, ethylene vinylacetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methylacrylate, copolymers of acrylic acid, polymethylmethacrylate or anyother polymers polymerizable by a high-pressure free radical process,polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer,styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH),polymers of aromatic monomers such as polystyrene, polyesters,polyacetal, polyvinylidine fluoride, polyethylene glycols, and/orpolyisobutylene.

In an embodiment, the polymer (or the polyethylene or polypropylene) ispresent in the above blends, at from 10 to 99 wt %, based upon theweight of the polymers in the blend, or 20 to 95 wt %, or at least 30 to90 wt %, or at least 40 to 90 wt %, or at least 50 to 90 wt %, or atleast 60 to 90 wt %, or at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g.,IRGAFOS 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

In an embodiment, any of the foregoing polymers, such as the foregoingpolypropylenes or blends thereof, may be used in a variety of end-useapplications. Applications include, for example, mono- or multi-layerblown, extruded, and/or shrink films. These films may be formed by anynumber of well known extrusion or coextrusion techniques, such as ablown bubble film processing technique, wherein the composition can beextruded in a molten state through an annular die and then expanded toform a uni-axial or biaxial orientation melt prior to being cooled toform a tubular, blown film, which can then be axially slit and unfoldedto form a flat film. Films may be subsequently unoriented, uniaxiallyoriented, or biaxially oriented to the same or different extents. One ormore of the layers of the film may be oriented in the transverse and/orlongitudinal directions to the same or different extents. The uniaxialorientation can be accomplished using typical cold drawing or hotdrawing methods. Biaxial orientation can be accomplished using tenterframe equipment or a double bubble processes and may occur before orafter the individual layers are brought together. For example, apolyethylene layer can be extrusion coated or laminated onto an orientedpolypropylene layer or the polyethylene and polypropylene can becoextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. Typically the films areoriented in the machine direction (MD) at a ratio of up to 15, orbetween 5 and 7, and in the transverse direction (TD) at a ratio of upto 15, or 7 to 9. However, In an embodiment the film is oriented to thesame extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In an embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In an embodiment, one or both of the surfacelayers is modified by corona treatment.

Molded Products

The compositions described herein (or polypropylene compositions) mayalso be used to prepare molded products in any molding process,including but not limited to, injection molding, gas-assisted injectionmolding, extrusion blow molding, injection blow molding, injectionstretch blow molding, compression molding, rotational molding, foammolding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

Further, the compositions described herein (or polypropylenecompositions) may be shaped into desirable end use articles by anysuitable means known in the art. Thermoforming, vacuum forming, blowmolding, rotational molding, slush molding, transfer molding, wet lay-upor contact molding, cast molding, cold forming matched-die molding,injection molding, spray techniques, profile coextrusion, orcombinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, CONCISEENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I.Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, orby calendaring. Sheets are generally considered to have a thickness offrom 254 μm to 2540 μm (10 mils to 100 mils), although any given sheetmay be substantially thicker.

Non-Wovens and Fibers

The polyolefin compositions described above may also be used to preparenonwoven fabrics and fibers of this invention in any nonwoven fabric andfiber making process, including but not limited to, melt blowing,spunbonding, film aperturing, and staple fiber carding. A continuousfilament process may also be used. Or a spunbonding process is used. Thespunbonding process is well known in the art. Generally it involves theextrusion of fibers through a spinneret. These fibers are then drawnusing high velocity air and laid on an endless belt. A calendar roll isgenerally then used to heat the web and bond the fibers to one anotheralthough other techniques may be used such as sonic bonding and adhesivebonding.

Accordingly, the instant disclosure relates to the followingembodiments:

A. A catalyst comprising a catalyst compound represented by the formula:

wherein:

M is a Group 3, 4, 5 or 6 transition metal;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;

each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; and

Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

B. The catalyst compound of embodiment A, wherein two or more of R¹ toR²⁸ independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.

C. The catalyst compound of embodiment A or B, wherein M is Hf, Ti, orZr.

D. The catalyst compound of embodiment A, B, or C wherein each X is,independently, a halogen or a C₁ to C₇ hydrocarbyl radical.

E. The catalyst compound of embodiment A, B, C, or D wherein each X is abenzyl radical.

F. The catalyst compound of embodiment A, B, C, D, or E wherein each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical.G. The catalyst compound of embodiment A, B, C, D, E, or F wherein eachR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl radical.H. The catalyst compound of embodiment A, B, C, D, E, F, or G whereinone or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, andR²⁸ is a methyl radical, a fluoride, or a combination thereof.I. The catalyst compound of embodiment A, B, C, D, E, F, G, or H,wherein Y is —CH₂CH₂— or 1,2-cyclohexylene.J. The catalyst compound of embodiment A, B, C, D, E, F, G, H, or I,wherein Y is —CH₂CH₂CH₂—.K. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, or Jwherein Y is a C₁-C₂₀ divalent hydrocarbyl radical comprising a linkerbackbone comprising from 1 to 18 carbon atoms bridging between nitrogenatoms N¹ and N².L. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, orK, wherein Y is a C₁-C₂₀ divalent hydrocarbyl radical comprising O, S,S(O), S(O)₂, Si(R′)₂, P(R′), N(R′), or a combination thereof, whereineach R′ is independently a C₁-C₁₈ hydrocarbyl radical.M. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, K,or L, wherein:

M is Zr;

X¹ and X² are benzyl radicals;

R¹ and R¹⁴ are methyl radicals;

R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and

Y is —CH₂CH₂—.

N. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, K,or L wherein:

M is Zr;

X¹ and X² are benzyl radicals;

R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;

R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are hydrogen; and

Y is —CH₂CH₂—.

O. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, K,or L wherein:

M is Zr;

X¹ and X² are benzyl radicals;

R¹ and R¹⁴ are methyl radicals;

R⁴ and R¹⁷ are fluoro groups;

R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are hydrogen; and

Y is —CH₂CH₂—.

P. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, K,or L wherein:

M is Zr;

X¹ and X² are benzyl radicals;

R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;

R⁸, R¹¹, R²¹ and R²⁴ are tert-butyl radicals;

R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²²,R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and

Y is —CH₂CH₂—.

Q. The catalyst compound of embodiment A, B, C, D, E, F, G, H, I, J, K,or L wherein:

M is Zr;

X¹ and X² are benzyl radicals;

R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;

R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;

R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²²,R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and

Y is —CH₂CH₂—.

R. A catalyst system comprising:

an activator and a catalyst compound represented by the formula:

where:M is a Group 3, 4, 5 or 6 transition metal;each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or a combination thereof, or X¹ and X² jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure,provided, however, where M is trivalent then X² is not present;each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; andY is a divalent C₁ to C₂₀ hydrocarbyl radical.R1. A catalyst system comprising an activator and a catalyst compound,wherein the catalyst compound is any one of the catalysts of embodimentsA through Q.S. The catalyst system of embodiment R or R1, wherein X¹ and X² jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure.T. The catalyst system of embodiment R, R1, or S, wherein the activatorcomprises alumoxane, a non-coordinating anion activator, or acombination thereof.U. The catalyst system of embodiment R, R1, S, or T, wherein theactivator comprises alumoxane and the alumoxane is present at a ratio of1 mole aluminum or more to mole of catalyst compound.V. The catalyst system of embodiment R, R1, S, T, or U, wherein theactivator is represented by the formula:(Z)d+(Ad−)

wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a neutralLewis base;

H is hydrogen;

(L-H)+ is a Bronsted acid;

Ad− is a non-coordinating anion having the charge d−; and

d is an integer from 1 to 3.

W. The catalyst system of embodiment R, R1, S, T, U, or V wherein theactivator is represented by the formula:(Z)d+(Ad−)wherein Ad− is a non-coordinating anion having the charge d−;d is an integer from 1 to 3, andZ is a reducible Lewis acid represented by the formula: (Ar3C+), whereAr is aryl radical, an aryl radical substituted with a heteroatom, anaryl radical substituted with one or more C₁ to C₄₀ hydrocarbylradicals, an aryl radical substituted with one or more functional groupscomprising elements from Groups 13-17 of the periodic table of theelements, or a combination thereof.X. The catalyst system of embodiment R, R1, S, T, U, V, or W, whereinthe activator is selected from the group consisting of:

-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   [4-tert-butyl-PhNMe2H][(C₆F₃ (C₆F₅)₂)₄B],-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(tert-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,-   tropillium tetraphenylborate,-   triphenylcarbenium tetraphenylborate,-   triphenylphosphonium tetraphenylborate,-   triethylsilylium tetraphenylborate,-   benzene(diazonium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   tropillium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   triethylsilylium tetrakis(pentafluorophenyl)borate,-   benzene(diazonium)tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,-   dimethyl(tert-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(tert-butyl)ammonium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate,-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(perfluorophenyl)borate,-   1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,-   tetrakis(pentafluorophenyl)borate,-   4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate),    and combinations thereof.    Y. A process to polymerize olefins comprising:    contacting one or more olefins with a catalyst system at a    temperature, a pressure, and for a period of time sufficient to    produce a polyolefin, the catalyst system comprising an activator    and a catalyst compound represented by the formula:

where:M is a Group 3, 4, 5 or 6 transition metal;each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof, or a combination thereof; andY is a divalent C₁ to C₂₀ hydrocarbyl.Y1. A process to polymerize olefins comprising:contacting one or more olefins with a catalyst system at a temperature,a pressure, and for a period of time sufficient to produce a polyolefin,the catalyst system comprising a catalyst compound according to any oneof embodiments A through Q.Y2. A process to polymerize olefins comprising:contacting one or more olefins with a catalyst system at a temperature,a pressure, and for a period of time sufficient to produce a polyolefin,wherein the catalyst system comprises any one of embodiments R, R1, or Sthrough X.Z. The process of embodiment Y, Y1, or Y2, wherein or two or more of R¹to R²⁸ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.AA. The process of embodiment Y, Y1, Y2, or Z, wherein the conditionscomprise a temperature of from about 0° C. to about 300° C., a pressurefrom about 0.35 MPa to about 10 MPa, and a time from about 0.1 minutesto about 24 hours.BB. The process of embodiment Y, Y1, Y2, Z, or AA, wherein the one ormore olefins comprise propylene.CC. The process of embodiment Y, Y1, Y2, Z, AA, or BB, wherein thepolyolefin comprises at least 50 mole % propylene.DD. A catalyst comprising a catalyst compound represented by theformula:

wherein:

A and A′ are heteroaryl radicals;

M is a Group 3, 4, 5 or 6 transition metal;

each X is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, provided, however, where M istrivalent then X² is not present;

each R¹, R², R³, R⁴, R⁵, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁷, and R²⁸ isindependently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R²⁸ may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure, or a combinationthereof; and

Y and Z together form a divalent C₁ to C₂₀ hydrocarbyl radical.

EE. The catalyst compound of embodiment DD wherein A and A′ eachcomprise carbazole radicals.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Thirteen illustrative catalystcompounds (A through M), each according to one or more embodimentsdescribed, were synthesized and used to polymerize olefins. Allreactions were carried out under a purified nitrogen atmosphere usingstandard glovebox, high vacuum or Schlenk techniques, unless otherwisenoted. All solvents used were anhydrous, de-oxygenated and purifiedaccording to known procedures. All starting materials were eitherpurchased from Aldrich and purified prior to use or prepared accordingto procedures known to those skilled in the art. Comparative catalystcompound C1 was synthesized as described in WO 03/091292A2.

Synthesis of Compounds A-M

9-(2-Methoxymethyletherphenyl)-9H-carbazole (1)

Copper (I) iodide (190 mg, 1 mmol), potassium phosphate tribasic (4.46g, 21 mmol) and racemic trans-1,2-diaminocyclohexane (228 mg, 2 mmol)were combined and dry 1,4-dioxane added. After stirring at roomtemperature for 5 minutes, 1-bromo-2-(methoxymethoxy)benzene (2.17 g, 10mmol) and carbazole (2.17 g, 13 mmol) were added and the contents heatedto reflux for 30 hours. The reaction was cooled to room temperature, anddiluted with dichloromethane. The mixture was filtered and the solutionwas concentrated. The resulting solid was diluted with acetone, filteredand the resulting solid was dried to give compound 1 (1.35 g, 45% yield)as a yellow solid.

2-(9H-Carbazol-9-yl)-phenol (2)

10.0 g (33.0 mmol) of compound 1 was slurried in a 2:1 mixture of THFand methanol and neat hydrochloric acid (28.9 g, 792 mmol) was added.After stirring at room temperature for 16 hours, the reaction wasquenched with saturated NaHCO₃ solution and extracted with two 100 mLportions of diethyl ether. The organic fractions were combined and driedover MgSO₄ and the solvent removed to give compound 2 as a brown oil(6.44 g, 75% yield).

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-phenol)(3)

A flask was charged with 2 (1.70 g, 6.56 mmol) and anhydrous ethanoladded. To this, paraformaldehyde (800 mg, 26.6 mmol) andN,N′-dimethylethylenediamine (0.35 mL, 3.28 mmol) were added and thecontents of the flask heated to reflux for 16 hours. The reaction wasthen cooled to room temperature and the solvent removed. The resultingoil was purified by flash chromatography (5:1 hexanes/ethyl acetate) toyield compound 3 as a white solid (673 mg, 40% yield).

9-(2-Methoxy-5-methylphenyl)-9H-carbazole (4)

2-Bromo-4-methylanisole (20.11 g, 100 mmol, 1 equiv) and carbazole(20.06 g, 120 mmol, 1.2 equiv) were dissolved in 1,4-dioxane (400 mL).Potassium phosphate tribasic (37.15 g, 175 mmol, 1.75 equiv), copper (I)iodide (0.95 g, 5 mmol, 0.05 equiv) and racemictrans-1,2-diaminocyclohexane (2.4 mL, 20 mmol, 0.2 equiv) were added andthe reaction was refluxed for two days. The reaction was cooled to roomtemperature, then partitioned with ethyl acetate (200 mL) and water (300mL). The aqueous layer was extracted with ethyl acetate (3×200 mL). Thecombined organic layers were washed with saturated brine, dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (150 g), eluting with 3% ethylacetate in heptanes to give compound 4 (13.5 g, 45% yield) as a yellowsolid.

2-(9H-Carbazol-9-yl)-4-methylphenol (5)

A 1.0 M boron tribromide solution in dichloromethane (90 mL, 90 mmol,1.9 equiv) was added dropwise at −78° C., over 30 minutes, to a solutionof compound 4 (13.5 g, 46.98 mmol, 1 equiv) in anhydrous dichloromethane(400 mL). The reaction was warmed to room temperature, when liquidchromatography-mass spectrometry (LCMS) indicated that the reaction wascomplete. The reaction was quenched with ice-water (200 mL). The layerswere separated and the aqueous phase was extracted with dichloromethane(2×100 mL). The combined organic layers were dried over sodium sulfate,filtered, and concentrated under reduced pressure. The residue waspurified on an ANALOGIX 40-150 g column, eluting with a gradient of 0 to20% ethyl acetate in heptanes to give compound 5 (12.3 g, 95% yield) asa yellow oil.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-methylphenol)(6)

A mixture of compound 5 (3.4 g, 12.44 mmol, 2 equiv), paraformaldehyde(1.87 g, 62.2 mmol, 10 equiv), N,N′-dimethylethylenediamine (0.67 mL,6.22 mmol, 1 equiv) and anhydrous ethanol (100 mL) was refluxed for 18hours. The reaction was cooled to room temperature, and thenconcentrated under reduced pressure. The residue was purified on anANALOGIX 25-60 g column, eluting with a gradient of 0 to 30% ethylacetate in heptanes to give compound 6 (1.1 g, 27% yield) as a whitesolid.

9-(5-Fluoro-2-methoxyphenyl)-9H-carbazole (7)

2-Bromo-4-fluoroanisole (20 g, 10 mmol, 1 equiv) and carbazole (18.4 g,11 mmol, 1.1 equiv) were dissolved in 1,4-dioxane (200 mL). Potassiumphosphate tribasic hydrate (46 g, 20 mmol, 2 equiv), copper(I) iodide (1g, 0.5 mmol, 0.05 equiv) and 1,2-diaminopropane (1 mL, 1.3 mmol, 0.13equiv) were added and the reaction was refluxed for 18 hours. Thereaction was cooled to room temperature and filtered through celite. Thefiltrate was concentrated under reduced pressure and the residue waspurified over silica gel (250 g), eluting with gradient of 0 to 10%ethyl acetate in heptanes to give compound 7 (7.6 g, 26% yield) as anoff white solid that was contaminated with carbazole.

2-(9H-Carbazol-9-yl)-4-fluorophenol (8)

A 1.0 M boron tribromide solution in dichloro-methane (60 mL, 60 mmol, 3equiv) was added dropwise over 30 minutes at −78° C. to a solution ofcompound 7 (5.8 g, 20 mmol, 1 equiv) in dichloromethane (60 mL). Thereaction was stirred at −78° C. for 4 hours, when ¹H-NMR indicated thatthe reaction was complete. The reaction was poured into saturated sodiumbicarbonate (100 mL) and the pH adjusted to 8 with 10% sodium hydroxide.The layers were separated and the aqueous phase was extracted withdichloro-methane (3×20 mL). The combined organic layers were dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (100 g), eluting with a gradient of60 to 100% dichloromethane in heptanes. The product containing fractionswere combined, concentrated under reduced pressure and triturated with20% methyl tert-butyl ether in heptanes (10 mL) to give compound 8 (4.3g, 78% yield) as a white solid.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-fluorophenol)(9)

A mixture of compound 8 (1.5 g, 5.4 mmol, 2 equiv), paraformaldehyde(716 mg, 5.4 mmol, 2 equiv), N,N′-dimethylethylenediamine (300 μL, 2.7mmol, 1 equiv) and anhydrous ethanol (20 mL) was refluxed for 18 hours(reaction was ˜60% complete after 2 hours). The reaction was cooled toroom temperature, then concentrated under reduced pressure. The residuewas purified over silica gel (50 g), eluting with a gradient of 60 to100% dichloromethane in heptanes to give compound 9 (640 mg, 34% yield)as a white solid.

9-(2-Methoxy-5-methylphenyl)-9H-(3,6-di-tert-butyl-carbazole) (10)

Racemic trans-1,2-diaminocyclohexane (5.12 mL, 42.6 mmol, 0.2 equiv),potassium phosphate tribasic (79.2 g, 372 mmol, 1.75 equiv) andcopper(I) iodide (2.03 g, 10.7 mmol, 0.05 equiv) were added at roomtemperature to a mixture of 2-bromo-4-methylanisole (42.9 g, 213 mmol,1.0 equiv) and 3,6-di-tert-butyl-9H-carbazole (65.5 g, 234 mmol, 1.1equiv) in 1,4-dioxane (1000 mL), which was degassed with a stream ofnitrogen for 15 minutes. The mixture was refluxed for four days, atwhich point LCMS indicated 40% conversion to product. After cooling toroom temperature, the mixture was diluted with water (500 mL) and ethylacetate (1000 mL). The layers were separated and the aqueous layer wasextracted with ethyl acetate (3×500 mL). The combined organic layerswere washed with saturated brine (500 mL), dried over sodium sulfate,filtered, and concentrated under reduced pressure. The crude product wastriturated with a 1:1 mixture of methyl tert-butyl ether and heptanes(500 mL) to give pure product. The mother liquor was purified on aBIOTAGE-75 L column, eluting with a gradient of 5 to 10% ethyl acetatein heptanes to give additional pure product. The two batches werecombined to give compound 10 (34.5 g, 37% yield) as an off-white solid.

2-(9H-(3,6-di-tert-butyl-Carbazol-9-yl))-4-methylphenol (11)

1.0M boron tribromide in dichloromethane (173 mL, 173 mmol, 2.0 equiv)was added dropwise at −70° C. to a solution of compound 10 (34.5 g, 86.5mmol, 1.0 equiv) in anhydrous dichloromethane (700 mL). The mixture wasallowed to warm to room temperature at which point LCMS indicated thatthe reaction was complete. The reaction was quenched by the slowaddition of ice-water (200 mL) and the layers were separated. Theaqueous layer was extracted with dichloromethane (2×200 mL), and thecombined organic layers were washed with saturated brine (200 mL), driedover sodium sulfate, filtered, and concentrated under reduced pressure.The residue was purified over silica gel (500 g) with dry-loading,eluting with a gradient of 0 to 20% ethyl acetate in heptanes to givethe desired product (31 g, ˜85% purity) as an off-white solid. Thismaterial was triturated with 5% ethyl acetate in heptanes (100 mL) togive compound 11 (18.9 g) as a white solid.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-(3,6-di-tert-butyl-carbazol-9-yl))-4-methylphenol)(12)

compound 11 (2.07 g; 5.37 mmol), N,N′-dimethylethylenediamine (0.144 mL,0.118 g, 1.63 mmol) and paraformaldehyde (0.161 g, 5.36 mmol) weredissolved in 40 mL of ethanol and refluxed overnight. The reactionmixture was allowed to cool to room temperature. The volatiles wereremoved under vacuum to give a pale yellow solid. Flash chromatographyusing a gradient of 40-100% dichloromethane/hexanes yielded compound 12(0.95 g) as an off-white solid (40% yield).

(2-Methoxy-5-methylphenyl)-9H-(3,6-di-mesityl-carbazole) (13)

Racemic trans-1,2-diaminocyclohexane (1.76 mL, 14.6 mmol, 0.2 equiv),potassium phosphate tribasic (27.2 g, 128 mmol, 1.75 equiv) and copper(I) iodide (0.7 g, 3.66 mmol, 0.05 equiv) were added at room temperatureto a mixture of 2-bromo-4-methylanisole (14.7 g, 73.2 mmol, 1.0 equiv)and 3,6-dimesityl-9H-carbazole (35.5 g, 87.8 mmol, 1.2 equiv) in1,4-dioxane (700 mL), which was degassed with a stream of nitrogen for15 minutes. The mixture was refluxed for five days, at which point LCMSindicated 60% conversion to product. After cooling to room temperature,the mixture was diluted with water (500 mL) and ethyl acetate (700 mL).The layers were separated and the aqueous layer was extracted with ethylacetate (3×500 mL). The combined organic layers were washed withsaturated brine (500 mL), dried over sodium sulfate, filtered, andconcentrated under reduced pressure. The crude product was purified oversilica gel (500 g), eluting with a gradient of 0 to 75% ethyl acetate inheptanes. The fractions containing product were combined, andconcentrated under reduced pressure to a volume of ˜400 mL. Theresulting solids were collected by vacuum filtration and the filter cakewas washed with heptanes (100 mL) to give compound 13 (20.0 g, 52%yield) as an off-white solid.

2-(9H-(3,6-di-Mesityl-carbazol-9-yl))-4-methylphenol (14)

1.0 M boron tribromide in dichloromethane (114 mL, 114 mmol, 2.0 equiv)was added dropwise at −70° C. to a solution of compound 13 (29.8 g, 56.9mmol, 1.0 equiv) in anhydrous dichloromethane (600 mL). The mixture wasallowed to warm to room temperature at which point LCMS indicated thatthe reaction was complete. The reaction was quenched by the slowaddition of ice-water (200 mL) and the layers were separated. Theaqueous layer was extracted with dichloromethane (2×200 mL) and thecombined organic layers were washed with saturated brine (200 mL), driedover sodium sulfate, filtered, and concentrated under reduced pressure.The residue was purified over silica gel (500 g) with dry-loading,eluting with a gradient of 0 to 10% ethyl acetate in heptanes to givecompound 14 (28.9 g, 99% yield) as a foamy solid.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-(3,6-di-mesityl-carbazol-9-yl))-4-methylphenol)(15)

compound 14 (2.213 g, 4.34 mmol), N,N′-dimethylethylene diamine (2.33mL, 0.191 g, 2.17 mmol) and paraformaldehyde (0.576 g, 19.2 mmol) weredissolved in 40 mL of ethanol and refluxed overnight. The reactionmixture was allowed to cool to room temperature. The volatiles wereremoved under vacuum to give a yellow residue. Flash chromatography witha gradient of 40-100% dichloromethane/hexanes gave compound 15 as anoff-white solid (1.10 g, 45% yield).

6,6′-(1E,1′E)-(cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)bis(2-(9H-carbazol-9-yl)phenol)(16)

A 250 mL round bottom flask was charged with2-(9H-carbazol-9-yl)-salicylaldehyde (1.0 g, 3.48 mmol) and ethanol wasadded. Cyclohexane-1,2-diamine (0.21 mL, 1.74 mmol) was added dropwise,and the vessel was closed and heated to 60° C. for 48 hours. Thereaction contents were concentrated and the crude product was purifiedby flash chromatography (10:1 hexanes:ethyl acetate). The organicfractions were collected, concentrated and recrystallized from hexanesto give the desired product 16 (1.69 g, 74% yield).

6,6′-((1,2-Cyclohexane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-phenol)(17)

A 250 mL round bottom flask was charged with compound 16 (1.69 g, 2.59mmol) dissolved in dichloromethane and allowed to stir under inert N₂atmosphere. To the solution, aqueous formaldehyde (3.78 mL, 46.62 mmol)was added, and the reaction mixture was cooled to 0° C. via an ice bath.While the chilled mixture was stirred vigorously, sodiumtriacetoxyborohydride (9.88 g, 46.62 mmol) was added in small batches,allowing for gas evolution to dissipate. The reaction was allowed towarm to room temperature, and stirred for 16 hours. The reaction wasquenched with 100 mL of water, and 50 mL of dichloromethane. The pH ofthe reaction was adjusted to pH=10-11 by addition of KOH. The reactionproduct was then extracted with dichloromethane (3×50 mL) and brine(1×20 mL). The organic extracts were dried over MgSO₄ and concentratedunder vacuum. The resulting oil was dissolved in acetonitrile, andprecipitated with hexanes to give the desired product 17 (1.11 g, 63%yield).

6,6′-((1,3-propyl-1,3-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-phenol)(18)

A 250 mL 2-neck round-bottom Schlenk flask was charged with2-carbazole-phenol (2) (3.00 g, 11.6 mmol), dissolved in methanol, and asmall amount of dichloromethane under an inert N₂ atmosphere. To thesolution, N,N′-dimethylpropylenediamine (0.94 mL, 5.78 mmol) and 37%aqueous formaldehyde (0.71 mL, 11.6 mmol) were added. A Dean-Starkcondenser was attached to the flask, and the reaction was refluxed at65° C. for 18 hours. Upon cooling, a precipitate formed on the sides ofthe flask. The reaction was further chilled to 0° C. and placed in thefreezer for 2 hours. The filtrate was collected from the solution, andfurther dried under vacuum to give the desired product 18 (2.75 g, 37%yield).

[6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)phenol)]zirconium(IV)dibenzyl(A)

Under a nitrogen atmosphere, a toluene solution (5 mL) of 3 (107 mg,0.17 mmol) was added to a yellow toluene solution (5 mL) of ZrBz₄ (77mg, 0.17 mmol), forming a deep yellow solution. After stirring at roomtemperature for 15 minutes, the solvent was removed to give a yellowsticky solid. The product was washed with pentane and dried under vacuumto give compound A as a yellow solid (yield 135 mg, 88%). Compounds Bthrough M were made in a similar manner from compounds 6, 9, 12, 15, 17or 18 and the corresponding Group 4 tetrabenzyl precursors.

[6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)phenol)]zirconium(IV)bis(tert-butoxide)(N)

(35 mg, 0.05 mmol) of 3 was dissolved in about 1 mL of diethyl ether andthe solution was added dropwise to a stirring solution of Hf(OtBu)₄ (25mg, 0.05 mmol) in about 1 mL of diethyl ether. The reaction mixture wasstirred for 2 hours and the solvent was thereafter removed under vacuum,yielding a white solid, which was washed with about 1 mL of pentane anddried in vacuo. The final yield was 52 mg (100%) of compound N. Suitablecrystals for X-ray analysis was grown in cold (−35° C.) toluene.

Polymerization Process:

Ethylene/1-octene copolymerizations were carried out in a parallelpressure reactor, which is described in U.S. Pat. Nos. 6,306,658,6,455,316 and 6,489,1681; WO 00/09255; and Murphy et al., J. Am. Chem.Soc., 2003, 125, 4306-4317, each of which is incorporated herein byreference. A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor, whichcontained 48 individual reaction vessels. The reactor was then closedand each vessel was individually heated to a set temperature (usually 70or 100° C.) and pressurized to a pre-determined pressure of ethylene(generally 0.93 MPa (135 psig)). 1-Octene (100 uL, 637 umol) wasinjected into each reaction vessel through a valve, followed by 500 uLof isohexane. Five hundred equivalents of methylalumoxane solution (30wt % in toluene) were then added to act as a co-catalyst/scavenger. Inan embodiment, for NCA activation, 50 equivalents of tri-n-octylaluminumwere added to act as a scavenger, followed by a toluene solution of anon-coordinating anion as described above. The contents of the vesselwere then stirred at 800 rpm. A toluene solution of catalyst (A-M andC1, 0.20 mmol/L, 5-20 nmol) and another aliquot of isohexane (500 uL)were then added to the reactor. All runs were performed in triplicate.While maintaining ethylene pressure in each reaction vessel at thepre-set level by computer control, the reaction was then allowed toproceed until a set time limit (usually 30 min) or until a set amount ofethylene had been taken up by the reaction. At this point, the reactionwas quenched by exposure to air. After the polymerization reaction, theglass vial insert containing the polymer product and solvent wereremoved from the pressure cell and the inert atmosphere glovebox, andthe volatile components were removed using a GENEVAC HT-12 centrifugeand GENEVAC VC3000D vacuum evaporator operating at elevated temperatureand reduced pressure. The vial was then weighed to determine the yieldof the polymer product. The resultant polymer was analyzed by Rapid GPC(see below) to determine the molecular weight, by FT-IR (see below) todetermine comonomer incorporation, and by differential scanningcalorimetry (DSC, see below) to determine melting point.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816,6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409,6,454,947, 6,260,407 and 6,294,388 each of which is incorporated hereinby reference. This apparatus had a series of three 30 cm×7.5 mm linearcolumns, each containing PLgel 10 um, Mix B. The GPC system wascalibrated using polystyrene standards ranging from 580-3,390,000 g/mol.The system was operated at an eluent flow rate of 2.0 mL/min and an oventemperature of 165° C. 1,2,4-Trichlorobenzene was used as the eluent.The polymer samples were dissolved in 1,2,4-trichlorobenzene at aconcentration of 0.1-0.9 mg/mL. Polymer solution (250 uL) was injectedinto the system. The concentration of the polymer in the eluent wasmonitored using an evaporative light scattering detector. The molecularweights obtained are relative to linear polystyrene standards.

Differential Scanning calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./min and then cooled at a rate of 50° C./min.Melting points were collected during the heating period.

The ratio of 1-octene to ethylene incorporated in the polymers (weight%) was determined by rapid FT-IR spectroscopy on a BRUKER EQUINOX 55+ IRin reflection mode. Samples were prepared in a thin film format byevaporative deposition techniques. Weight % 1-octene was obtained fromthe ratio of peak heights at 1378 and 4322 cm⁻¹. This method wascalibrated using a set of ethylene/1-octene copolymers with a range ofknown wt % 1-octene content.

Polymerization data shown in Table 1 is intended to be representative ofthe catalytic behavior of compounds A-M and C1 and is not intended to becomprehensive.

TABLE 1 Selected High Throughput Polymerization Results Amount TempPressure Time Yield Activity Mw MWD Incorporation Tm Run CatalystActivator (nmol) (° C.) (psi) (sec) (mg) (g/mmol h bar) (kDa) (Mw/Mn)(wt %) (° C.) 1 A MAO 20 75 135 8 238 574,000 12 1.7 9.2 116 2 A MAO 2075 135 6 215 694,000 12 1.7 11.0 116 3 A MAO 20 75 135 8 243 589,000 141.7 10.9 117 4 A MAO 20 100 135 8 177 429,000 12 1.6 12.7 116 5 A MAO 20100 135 9 182 390,000 12 1.7 9.7 116 6 A MAO 20 100 135 8 174 421,000 131.8 11.8 116 7 B MAO 20 75 135 7 217 599,000 12 1.8 21.7 ND 8 B MAO 2075 135 8 199 480,000 12 1.7 23.6 ND 9 B MAO 20 75 135 7 209 577,000 131.8 26.7 ND 10 B MAO 20 100 135 7 155 427,000 11 1.7 29.0 ND 11 B MAO 20100 135 7 156 431,000 12 1.7 25.8 ND 12 B MAO 20 100 135 7 156 431,00011 1.7 27.9 ND 13 C MAO 20 75 135 13 131 194,000 52 1.7 5.5 120 14 C MAO20 75 135 16 146 177,000 52 1.7 8.0 121 15 C MAO 20 75 135 10 89 171,00050 1.7 9.4 116 16 C MAO 20 100 135 13 107 159,000 45 1.7 8.5 117 17 CMAO 20 100 135 13 106 158,000 47 1.6 9.4 118 18 C MAO 20 100 135 13 97144,000 45 1.6 9.2 118 19 D MAO 20 75 135 1802 31 337 3916 1.3 10.4 11020 D MAO 20 75 135 1802 35 376 3969 1.3 20.9 110 21 D MAO 20 75 135 180134 367 3898 1.3 33.6 110 22 D MAO 20 100 135 1800 9 99 ND ND ND ND 23 DMAO 20 100 135 1800 9 98 ND ND ND ND 24 D MAO 20 100 135 1802 6 68 ND NDND ND 25 D NCA 20 70 135 982 36 717 4587 1.2 8.2 112 26 D NCA 20 70 135789 32 787 4400 1.2 7.9 113 27 D NCA 20 70 135 1051 36 660 4720 1.2 9.4112 28 D NCA 20 90 135 1801 18 194 3701 1.3 9.8 110 29 D NCA 20 90 1351800 18 194 3864 1.3 8.5 110 30 D NCA 20 90 135 1800 15 165 3597 1.3 8.5110 31 E MAO 20 75 135 6 190 610,000 9 1.6 23.0 115 32 E MAO 20 75 135 8217 524,000 9 1.7 24.9 115 33 E MAO 20 75 135 6 224 721,000 9 1.7 25.2114 34 E MAO 20 100 135 11 139 244,000 7 1.5 22.3 102 35 E MAO 20 100135 11 148 260,000 8 1.9 25.4 103 36 E MAO 20 100 135 18 157 168,000 81.6 17.5 102 37 E NCA 10 70 135 6 167 1,077,000 11 1.5 23.4 119 38 E NCA10 70 135 8 204 986,000 11 1.6 34.3 119 39 E NCA 10 70 135 8 198 955,00011 1.6 18.1 119 40 E NCA 10 90 135 8 133 640,000 10 1.5 223.0 117 41 ENCA 10 90 135 8 131 632,000 11 1.6 23.3 117 42 E NCA 10 90 135 12 143459,000 10 1.5 24.1 117 43 G MAO 20 75 135 6 187 603,000 11 1.7 21.1 11744 G MAO 20 75 135 6 208 670,000 13 1.9 22.1 117 45 G MAO 20 75 135 8211 509,000 13 1.6 18.4 118 46 G MAO 20 100 135 8 172 415,000 12 1.619.9 115 47 G MAO 20 100 135 8 175 423,000 14 1.8 18.6 115 48 G MAO 20100 135 8 172 416,000 12 1.7 20.4 115 49 H MAO 20 75 135 21 139 128,00073 1.6 7.8 120 50 H MAO 20 75 135 20 141 136,000 69 1.7 6.6 119 51 H MAO20 75 135 20 141 136,000 72 1.7 7.8 120 52 H MAO 20 100 135 10 108210,000 57 1.7 11.4 117 53 H MAO 20 100 135 10 115 222,000 59 1.6 13.7117 54 H MAO 20 100 135 10 110 212,000 58 1.6 13.9 116 55 I MAO 20 75135 8 223 538,000 10 1.8 20.6 114 56 I MAO 20 75 135 6 206 665,000 111.7 29.2 115 57 I MAO 20 75 135 8 215 519,000 12 1.8 26.6 115 58 I MAO20 100 135 8 186 449,000 10 1.6 22.4 114 59 I MAO 20 100 135 8 183443,000 10 1.7 26.1 113 60 I MAO 20 100 135 5 178 689,000 9 1.6 22.7 11361 J MAO 20 75 135 18 140 151,000 129 1.8 6.9 123 62 J MAO 20 75 135 18141 150,000 125 1.7 7.0 123 63 J MAO 20 75 135 18 135 145,000 121 1.65.3 123 64 J MAO 20 100 135 13 95 141,000 121 1.7 5.6 120 65 J MAO 20100 135 16 109 131,000 141 1.8 4.9 121 66 J MAO 20 100 135 16 97 117,000132 1.8 5.3 121 67 K MAO 20 75 135 38 94 47,600 363 1.6 4.8 120 68 K MAO20 75 135 44 123 54,100 308 1.5 6.4 118 69 K MAO 20 75 135 42 123 56,700321 1.7 6.4 119 70 K MAO 20 100 135 38 84 42,700 337 1.5 6.8 116 71 KMAO 20 100 135 37 89 46,200 311 1.4 6.4 116 72 K MAO 20 100 135 98 234600 329 1.5 5.2 120 73 L MAO 20 75 135 1802 6 70 ND ND ND ND 74 L MAO20 75 135 1801 6 70 ND ND ND ND 75 L MAO 20 75 135 1800 6 70 ND ND ND ND76 L MAO 20 100 135 1802 4 40 ND ND ND ND 77 L MAO 20 100 135 1801 4 40ND ND ND ND 78 L MAO 20 100 135 1800 4 40 ND ND ND ND 79 M MAO 20 75 1351802 13 140 ND ND ND ND 80 M MAO 20 75 135 1800 10 110 ND ND ND ND 81 MMAO 20 75 135 1800 9 90 ND ND ND ND 82 M MAO 20 100 135 1802 7 70 ND NDND ND 83 M MAO 20 100 135 1802 6 60 ND ND ND ND 84 M MAO 20 100 135 18016 60 ND ND ND ND 85 C1 MAO 20 75 135 40 124 60,100 15 1.6 8.0 125 86 C1MAO 20 75 135 37 139 72,700 15 1.7 8.4 124 87 C1 MAO 20 75 135 37 15480,300 15 1.6 10.1 124 88 C1 MAO 20 100 135 24 105 84,800 13 1.6 9.0 12389 C1 MAO 20 100 135 1800 0 0 ND ND ND ND 90 C1 MAO 20 100 135 19 9799,100 13 1.7 10.9 123 Notes: ND = Not Determined

Larger scale lab propylene polymerizations were carried out as follows:approximately 10 mg of solid catalyst (˜0.01 mmol) and 500 equivalentsof solid methylalumoxane (˜330 mg) were weighed out and placed in a 100mL steel reaction flask. Propylene was condensed at −85° C. in a coldbath and approximately 25 g of liquid propylene was poured onto themixture of solid catalyst and methylalumoxane. The flask was then sealedand either left to warm to room temperature with stirring for 16 hours,or heated to 70° C. for one hour. The contents of the flask were thenvented and the solid polypropylene collected and weighed.

Molecular weight distribution was characterized using a high temperaturesize exclusion chromatograph (WATERS ALLIANCE 2000) equipped with adifferential refractive index detector (DRI). Three POLYMER LABORATORIESPLgel 10 mm Mixed-B columns were used. The nominal flow rate was 1.0mL/min, and the nominal injection volume was 300 uL. The varioustransfer lines, columns and the DRI detector were contained in an ovenmaintained at 145° C. Polymer solutions were prepared by dissolving thedesired amount of dry polymer in the appropriate volume of1,2,4-trichlorobenzene to yield concentrations ranging from 0.25 to 1.5mg/mL. The sample mixtures were heated at 160° C. with continuousagitation for ˜2 hours. The solution was filtered through a 2 micronstainless steel filter (POLYMER LABS) into scintillation vials using aPOLYMER LABS SP260 sample prep station. The separation efficiency of thecolumn set was calibrated using a series of narrow MWD polystyrenestandards (POLYMER LABORATORIES), which reflects the expected MW rangefor samples and the exclusion limits of the column set. Seventeenindividual polystyrene standards, ranging from Mp ˜580 to 10,000,000,were used to generate the calibration curve.

Differential scanning calorimetry (DSC) measurements were performed on aPERKIN ELMER PYRIS 1 instrument to determine the melting point of thepolymers. Samples were heated to 200° C. for 10 minutes and then cooledto −20° C. at a rate of 10° C./min. After being held at this temperaturefor 10 minutes, they were then heated to 200° C. at a rate of 10°C./min. Melting points were collected during the heating period.

TABLE 2 Selected Batch Polymerization Results Monomer Amount Temp AmountTime Yield Activity Mw MWD Tm Run Catalyst Activator (mg) (° C.) (g)(hr) (g) (g/mmol h) (kDa) (Mw/Mn) (° C.) 91 A MAO 12 70 22.7 1 4.5 3381.76 1.76 92 B MAO 10 70 25.1 1 11.4 1065 93 C MAO 13 70 22.5 1 2.6 19894 D MAO 12 25 23.1 16 4.0 18 1335 2.07 95 D MAO 12 70 23.5 1 0.57 431102 2.52 96 E MAO 12 25 25.1 15 20.7 107 2.04 2.44 97 E MAO 12 70 24.21 6.56 513 1.41 2.65 98 E NCA 15 70 23.4 1 15.6 957 1.37 2.24 99 E NCA 770 14.0 1 4.06 544 0.99 2.16 100 F^(a) MAO 5 25 7.64 12 3.47 101 G MAO13 70 24.2 1 15.8 1392 3.28 2.07 102 H MAO 14 70 25.9 1 14.0 1223 15.92.38 103 I MAO 15 70 25.0 1 8.54 804 0.53 2.15 104 J MAO 13 70 23.8 17.15 510 105 K MAO 10 70 22.5 1 7.25 742 24.1 3.72 106 M MAO 15 70 24.11 0 0 ND ND ND 107 C1 MAO 15 70 25.7 1 0.94 62 Notes: ND = notdetermined, ^(a)= [mmmm] = 71.4Crystal Data:

X-Ray crystallography data for C₅₀H₅₂F₂N₄O₄Hf (compound N) with onemolecule of toluene; M=1081.58; orthorhombic; space group P-21;a=19.0539(2), b=13.1113(2), c=20.3121(3) Å; α=90°, β=90°, γ=90°;V=5074.40(12) Å³; Z=4; Dc=1.416 g cm⁻³; μ(Mo—Kα)=2.113 mm⁻¹; T=110(2) K;No. of data collected 8649; R1=0.0543 and wR2=0.1129 for 7492reflections with I>2σ (I); R1=0.0652 and wR2=0.1170 for all reflections.The following are representations of the crystallographic structure ofcompound N with the tert-butyl groups on oxygen atoms 2 and 3 omittedfor clarity:

As the data show, the catalyst compounds, catalyst systems, andpolymerization processes disclosed herein provide novel and improvedcatalyst and systems for the polymerization of olefins, which producepolymers having improved properties, such as high polymer melting point,high polymer molecular weights, an increased conversion and/or comonomerincorporation, which may further include a significant amount of longchain branching and/or a significant amount of vinyl termination.

The catalysts in an embodiment provide improvement in catalyst activity,produce polymers with improved properties or both. In an embodimentcrystallographic techniques indicate that the appended ring system orsystems (e.g., the carbazole ring systems) are oriented transversely,e.g., perpendicular, to the phenol rings. In an embodiment thesecatalysts have a structure to provide a broad corridor for the polymerylmoiety to reside and for the monomer to insert during the polymerizationprocess. As such, catalysts according to one embodiment of the instantdisclosure provide for an ability to control one or more characteristicsof polymerization, tacticity, comonomer insertion, and the like.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.Likewise whenever a composition, an element or a group of elements ispreceded with the transitional phrase “comprising”, it is understoodthat we also contemplate the same composition or group of elements withtransitional phrases “consisting essentially of,” “consisting of”,“selected from the group of consisting of,” or “is” preceding therecitation of the composition, element, or elements and vice versa.

What is claimed is:
 1. A catalyst compound represented by the formula:

M is a Group 4, 5 or 6 transition metal; each X is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,and R²⁸ is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R²⁸ may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure,or a combination thereof; and Y is a divalent C₁ to C₂₀ hydrocarbylradical.
 2. The catalyst compound of claim 1 wherein two or more of R¹to R²⁸ independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 3. The catalyst compound of claim 1 wherein Mis Hf, Ti, or Zr.
 4. The catalyst compound of claim 1 wherein each X is,independently, a halogen or a C₁ to C₇ hydrocarbyl radical.
 5. Thecatalyst compound of claim 1 wherein each X is a benzyl radical.
 6. Thecatalyst compound of claim 1 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is independently, hydrogen, a halogen,or a C₁ to C₃₀ hydrocarbyl radical.
 7. The catalyst compound of claim 1wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, andR²⁸ is independently, hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbylradical.
 8. The catalyst compound of claim 1 wherein one or more of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is a methylradical, a fluoride, or a combination thereof.
 9. The catalyst compoundof claim 1 wherein Y is —CH₂CH₂— or 1,2-cyclohexylene.
 10. The catalystcompound of claim 1 wherein Y is —CH₂CH₂CH₂—.
 11. The catalyst compoundof claim 1 wherein Y is a C₁-C₂₀ divalent hydrocarbyl radical comprisinga linker backbone comprising from 1 to 18 carbon atoms bridging betweennitrogen atoms N¹ and N².
 12. The catalyst compound of claim 1 wherein Yis a C₁-C₂₀ divalent hydrocarbyl radical comprising O, S, S(O), S(O)₂,Si(R′)₂, P(R′), N(R′), or a combination thereof, wherein each R′ isindependently a C₁-C₁₈ hydrocarbyl radical.
 13. The catalyst compound ofclaim 1 wherein: M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ aremethyl radicals; R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and Yis —CH₂CH₂—.
 14. The catalyst compound of claim 1 wherein: M is Zr; X¹and X² are benzyl radicals; R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals; R²,R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are hydrogen; and Y is—CH₂CH₂—.
 15. The catalyst compound of claim 1 wherein: M is Zr; X¹ andX² are benzyl radicals; R¹ and R¹⁴ are methyl radicals; R⁴ and R¹⁷ arefluoro groups; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ arehydrogen; and Y is —CH₂CH₂—.
 16. The catalyst compound of claim 1wherein: M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴ and R¹⁷ aremethyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are tert-butyl radicals; R², R³,R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²², R²³, R²⁵and R²⁶ through R²⁸ are hydrogen; and Y is —CH₂CH₂—.
 17. The catalystcompound of claim 1 wherein: M is Zr; X¹ and X² are benzyl radicals; R¹,R⁴, R¹⁴ and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are mesitylradicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and Y is —CH₂CH₂—.18. A catalyst system comprising: an activator and a catalyst compoundrepresented by the formula:

where: M is a Group 4, 5 or 6 transition metal; each X is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or a combination thereof; or X¹ and X² join together to form aC₄ to C₆₂ cyclic or polycyclic ring structure; each R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is independently, a hydrogen,a C₁-C₄₀ hydrocarbyl radical, a functional group comprising elementsfrom Group 13-17 of the periodic table of the elements, or two or moreof R¹ to R²⁸ may independently join together to form a C₄ to C₆₂ cyclicor polycyclic ring structure, or a combination thereof; and Y is adivalent C₁ to C₂₀ hydrocarbyl radical.
 19. The catalyst system of claim18, wherein two or more of R¹ to R²⁸ independently join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure.
 20. The catalyst systemof claim 18, wherein the activator comprises alumoxane, anon-coordinating anion activator, or a combination thereof.
 21. Thecatalyst system of claim 18, wherein the activator comprises alumoxaneand the alumoxane is present at a ratio of 1 mole aluminum or more tomole of catalyst compound.
 22. The catalyst system of claim 18, whereinthe activator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein Z is (L-H), or a reducible Lewis Acid, whereinL is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid;A^(d−) is a non-coordinating anion having the charge d−; and d is aninteger from 1 to
 3. 23. The catalyst system of claim 18 wherein theactivator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein A^(d−) is a non-coordinating anion having thecharge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acidrepresented by the formula: (Ar₃C⁺), where Ar is aryl radical, an arylradical substituted with a heteroatom, an aryl radical substituted withone or more C₁ to C₄₀ hydrocarbyl radicals, an aryl radical substitutedwith one or more functional groups comprising elements from Groups 13-17of the periodic table of the elements, or a combination thereof.
 24. Thecatalyst system of claim 18 wherein the activator is selected from thegroup consisting of: trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), andcombinations thereof.
 25. A process to polymerize olefins comprising:contacting one or more olefins with a catalyst system at a temperature,a pressure, and for a period of time sufficient to produce a polyolefin,the catalyst system comprising an activator and a catalyst compoundrepresented by the formula:

where: M is a Group 4, 5 or 6 transition metal; each X is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴,R²⁵, R²⁶, R²⁷, and R²⁸ is independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or two or more of R¹ to R²⁸may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure, or a combination thereof; and Y is a divalent C₁ to C₂₀hydrocarbyl.
 26. The process of claim 25, wherein or two or more of R¹to R²⁸ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 27. The process of claim 25 whereinconditions of the contacting comprise a temperature of from about 0° C.to about 300° C., a pressure from about 0.35 MPa to about 10 MPa, and atime from about 0.1 minutes to about 24 hours.
 28. The process of claim25, wherein the one or more olefins comprise propylene.
 29. The processof claim 25 wherein the polyolefin comprises at least 50 mole %propylene.
 30. The process of claim 25 wherein M is Hf, Ti, or Zr. 31.The process of claim 25 wherein each X is, independently, a halogen or aC₁ to C₇ hydrocarbyl radical.
 32. The process of claim 25 wherein each Xis a benzyl radical.
 33. The process of claim 25 wherein each R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is, independently,hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical.
 34. The processof claim 25 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵,R²⁶, R²⁷, and R²⁸ is, independently, hydrogen, a halogen, or a C₁ to C₁₀hydrocarbyl radical.
 35. The process of claim 25 wherein one or more ofR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is amethyl radical, a fluoride, or a combination thereof.
 36. The process ofclaim 25 wherein Y is —CH₂CH₂— or 1,2-cyclohexylene.
 37. The process ofclaim 25 wherein Y is —CH₂CH₂CH₂—.
 38. The process of claim 25 wherein Yis a C₁-C₂₀ divalent hydrocarbyl radical comprising a linker backbonecomprising from 1 to 18 carbon atoms bridging between nitrogen atoms N¹and N².
 39. The process of claim 25 wherein Y is a C₁-C₂₀ divalenthydrocarbyl radical comprising O, S, S(O), S(O)₂, Si(R′)₂, P(R′), N(R′),or a combination thereof, wherein each R′ is independently a C₁-C₁₈hydrocarbyl radical.
 40. The process of claim 25 wherein: M is Zr; X¹and X² are benzyl radicals; R¹ and R¹⁴ are methyl radicals; R² throughR¹³ and R¹⁵ through R²⁸ are hydrogen; and Y is —CH₂CH₂—.
 41. The processof claim 25 wherein: M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸through R²⁸ are hydrogen; and Y is —CH₂CH₂—.
 42. The process of claim 25wherein: M is Zr; X¹ and X² are benzyl radicals; R¹ and R¹⁴ are methylradicals; R⁴ and R¹⁷ are fluoro groups; R², R³, R⁵ through R¹³, R¹⁵,R¹⁶, R¹⁸ through R²⁸ are hydrogen; and Y is —CH₂CH₂—.
 43. The process ofclaim 25 wherein: M is Zr; X¹ and X² are benzyl radicals; R¹, R⁴, R¹⁴and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴ are tert-butylradicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and Y is —CH₂CH₂—.44. The process of claim 25 wherein: M is Zr; X¹ and X² are benzylradicals; R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹ and R²⁴are mesityl radicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶,R¹⁸, R¹⁹, R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and Y is—CH₂CH₂—.
 45. The process of claim 25, wherein the activator comprisesalumoxane, a non-coordinating anion activator, or a combination thereof.46. The process of claim 25, wherein the activator comprises alumoxaneand the alumoxane is present at a ratio of 1 mole aluminum or more tomole of catalyst compound.
 47. The process of claim 25, wherein theactivator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein Z is (L-H), or a reducible Lewis Acid, whereinL is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid;A^(d−) is a non-coordinating anion having the charge d−; and d is aninteger from 1 to
 3. 48. The process of claim 25 wherein the activatoris represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein A^(d−) is a non-coordinating anion having thecharge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acidrepresented by the formula: (Ar₃C⁺), where Ar is aryl radical, an arylradical substituted with a heteroatom, an aryl radical substituted withone or more C₁ to C₄₀ hydrocarbyl radicals, an aryl radical substitutedwith one or more functional groups comprising elements from Groups 13-17of the periodic table of the elements, or a combination thereof.
 49. Theprocess of claim 25 wherein the activator is selected from the groupconsisting of: trimethylammonium tetrakis(perfluoronaphthyl)borate,triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), andcombinations thereof.